WO2003066751A1 - Composition d'encre et procede d'impression par jet d'encre - Google Patents

Composition d'encre et procede d'impression par jet d'encre Download PDF

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Publication number
WO2003066751A1
WO2003066751A1 PCT/JP2003/001070 JP0301070W WO03066751A1 WO 2003066751 A1 WO2003066751 A1 WO 2003066751A1 JP 0301070 W JP0301070 W JP 0301070W WO 03066751 A1 WO03066751 A1 WO 03066751A1
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Prior art keywords
group
general formula
dye
ink
substituted
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PCT/JP2003/001070
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English (en)
Japanese (ja)
Inventor
Manabu Ogawa
Nobuhiro Nishita
Keiichi Tateishi
Junichi Yamanouchi
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Fuji Photo Film Co., Ltd.
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Application filed by Fuji Photo Film Co., Ltd. filed Critical Fuji Photo Film Co., Ltd.
Priority to JP2003566110A priority Critical patent/JP4538228B2/ja
Priority to EP20030703149 priority patent/EP1473332B1/fr
Priority to US10/503,444 priority patent/US7311391B2/en
Publication of WO2003066751A1 publication Critical patent/WO2003066751A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to an ink composition having high quality of an obtained image, excellent storage stability, and excellent ejection stability, and an ink jet recording method using the ink composition.
  • Dyes used in inks have high solubility in solvents, high density recording is possible, good hue, and excellent fastness to light, heat, air, water and chemicals It must have good fixability to the image-receiving material, not easily bleeding, excellent storage stability as an ink, no toxicity, high purity, and availability at low cost. ing. However, it is extremely difficult to search for pigments that meet these requirements at a high level. In particular, a dye having a good cyan hue or a magenta evening hue and having excellent fastness is strongly desired.
  • Ink jet recording methods include a method in which pressure is applied by a piezo element to eject droplets, a method in which bubbles are generated in ink by heat to eject droplets, a method using ultrasonic waves, and a method using electrostatic force. There is a method of sucking and discharging droplets.
  • aqueous inks, oil-based inks, or solid (fused) inks are used. Of these inks, water-based inks are the mainstream in terms of manufacturing, handling, odor and safety.
  • Dyes that satisfy the above requirements are also required as dyes for use in ink jet recording inks, and various dyes and pigments have already been proposed and actually used. However, a dye that satisfies all requirements has not yet been discovered. Color With well-known dyes and pigments, such as those having an index (CI) number, it is difficult to achieve both the hue and robustness required for ink jet recording inks.
  • CI index
  • As a dye for improving fastness an azo dye derived from an aromatic amine and a 5-membered heterocyclic amine described in Japanese Patent Publication No. 55-161856 has been proposed. However, these dyes have unfavorable hues in the yellow and cyan regions, and thus have a problem of deteriorating color reproducibility.
  • JP-A-61-36362 and JP-A-2-212566 disclose ink jet recording inks aiming at achieving both hue and light fastness.
  • the dyes used in each of the publications have insufficient solubility in water when used as a water-soluble ink.
  • the dyes described in each of the publications are used as a water-soluble ink for an ink jet, there is a problem in fastness to wet heat.
  • Japanese Patent Application No. 2000-80733 describes an ink jet recording ink using virazolylanilinazo to further improve hue and light fastness.
  • these inks for recording ink jet recordings had insufficient color reproducibility and robustness of output images.
  • JP-A-58-74761 and JP-A-60-92369 disclose a dye, an ink composed of glycerin and diethylene glycol, and an ethylene oxide adduct of alcohol
  • Japanese Patent Publication No. 2000-265098 discloses a long-chain ink.
  • Inks using an ethylene oxide adduct of a chain alcohol have been proposed but are not sufficient, and have the disadvantage that the image quality of the image formed during storage is deteriorated.
  • 5,837,043 and 5,626,655 disclose the bleeding of an image with an ink using an addition product of higher alcohol ethylenoxide. It has been proposed that color can be reduced, but it still has drawbacks such as clogging and clogging, poor image storability after printing, and a change in color tone.
  • the properties required for dyes used in inks are: 1) good hue and no hue change (solpato); 2) excellent resistance (light, ozone, NOx, solvent, oil, water) 3) safe (no Ames, no carcinogenicity, no skin irritation, easy to decompose), 4) low cost, 5) high cost, 6) high solubility, 7) media On the other hand, it has strong adhesion.
  • ink and conk ink are required to be: 1) uniform regardless of temperature and aging, 2) resistant to contamination, 3) good penetration into media, 4) uniform droplet size, 5 ) Paper is not selected. 6) Easily prepared liquid. 7) There is no ejection mistake, bubbles are not easily formed, bubbles easily disappear, and 8) stable ejection is possible.
  • the requirements for images are 1) clean without bleeding, discoloration and beading, 2) scratch resistant, 3) high gloss and uniform, 4) good image storability Excellent fading balance; 5) fast drying; 6) high speed printing; and 7) no fading rate dependence on image density.
  • an object of the present invention is to obtain an ink composition that satisfies the above-mentioned requirements, and in particular, in view of the conventional problems described above, the present invention relates to an aqueous ink excellent in handleability, odor, safety, and the like. High ejection stability, good hue of the obtained image, excellent image storability such as resistance to light, heat, ozone, etc. and water resistance, no defects in image quality such as bleeding of fine lines, severe
  • Another object of the present invention is to provide an ink composition having good image storability even under conditions, especially an ink jet recording ink.
  • the present invention also aims to provide an ink jet recording method using the ink.
  • the above object of the present invention has been achieved by the following means.
  • At least one dye having an oxidation potential no higher than 1.0 V is dissolved or dispersed in an aqueous medium, and the surfactant is contained in an amount of 0.05 to 50 g / 1. Ink composition.
  • R 21 represents an alkyl group having 5 to 40 carbon atoms. Represents the average number of moles of ethylene oxide added, and is 2 to 40.
  • R 24 COO + CH 2 CH 20 ⁇ ⁇ ⁇ H
  • R 24 represents an alkyl group having 5 to 40 carbon atoms.
  • m 2 represents the average number of moles of ethylene oxide added, and is 2 to 40.
  • R 22 and R 23 each represent a saturated hydrocarbon having 4 to 10 carbon atoms, and the total number of carbon atoms of R 22 and R 23 is 8 to 18. Represents the average number of moles of ethylene oxide added, and is 3 to 20. 5.
  • R 25 is a saturated carbon dioxide having 2 to 20 carbon atoms
  • m 21 represents an average addition mole number of ethylene oxide, and 2 to 40 It is.
  • R 31 and R 32 each independently represent an alkyl group having 1 to 18 carbon atoms.
  • R 33 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • X is a hydrogen atom
  • R 34 R 35 each independently represents an alkyl group having 1 to 18 carbon atoms.
  • R 36 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • m 3 and m 4 each represent the average number of moles of ethylene oxide added, and m 3 + m 4 is 0 to 100.
  • R 37 , R 39 and R 40 each independently represent an alkyl group having 1 to 6 carbon atoms, and m 31 and m 41 each represent an average addition mole number of ethylene oxide. And m 31 + m 41 is from 0 to 40.
  • R 41 represents an alkyl group having 1 to 4 carbon atoms
  • R 42 represents an alkyl group having 2 to 3 carbon atoms
  • n represents an integer of 2 to 5.
  • the amount of Cu ions flowing out of the image into water is less than 20% of the total dye.
  • X is x 2 , x 3 and x 4 are each independently — so— z, — so 2 — z,- Or represents one C 0.
  • Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryl group.
  • R 1 ⁇ and R 2 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. If there are multiple Zs, They may be the same or different.
  • Y LS ⁇ 2 , ⁇ 3 and ⁇ 4 each independently represent a monovalent substituent.
  • Xi to X 4 When any one of is present, they may be the same or different.
  • a ⁇ a and ⁇ to 13 4 it it to display the number of substituents Xi ⁇ X 4 and Y to Y 4, ai ⁇ a 4, it it independently integers of 0 to 4, all at the same time It cannot be 0 and ⁇ ⁇ is an integer from 0 to 4 each independently.
  • M is a hydrogen atom, a metal atom or an oxide, hydroxide, or halide thereof.
  • X U to X 14 , Y U to Y 18 and M are Xi to X 4 of the general formula (C—I), And M and their synonyms.
  • Au ⁇ a 14 is therewith it independently represents an integer of 1 or 2.
  • A represents a 5-membered heterocyclic group.
  • R 5 and R 6 each independently represent a hydrogen atom or a substituent, and the substituent is an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Represents a rubamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and the hydrogen atom of each of the substituents may be substituted.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and the substituent is a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group , An alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, an acyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a silyloxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyl group Xy, aryloxycarbonyloxy, amino, acylamino, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkylsulfonylamino, Arylsulfonylamino group,
  • R 1 and R 5 , or R 5 and R 6 may combine to form a 5- to 6-membered ring.
  • An ink jet recording method in which an ink droplet is ejected to an image receiving material having an image receiving layer containing white inorganic pigment particles on a support in accordance with a recording signal, and an image is recorded on the image receiving material. 22. An ink jet recording method, comprising: the ink composition according to any one of 1 to 21 above. -Best mode for carrying out the invention
  • the use of a dye having an oxidation potential nobler than 1.0 V (preferably a dye nobler than 1. IV, particularly preferably a dye nobler than 1.2 V) provides image storability, An image having excellent ozone resistance can be obtained.
  • Eox oxidation potential
  • Sani ⁇ position is in a solvent such as dimethylformamide Ya Asetonitoriru containing supporting electrolyte such as sodium perchlorate and perchlorate tetrapropylammonium en Moniumu, the test sample 1 X 10- 4 ⁇ 1 X It was dissolved in a concentration of 10- 6 mol / Ridzutoru, It is measured as a value for SCE (saturated calomel electrode) using cyclic voltametry or DC polarography. This value may deviate by several tens of mil volts due to the effect of the liquid potential difference and the liquid resistance of the sample solution, but the reproducibility of the potential can be guaranteed by inserting a standard sample (for example, hydroquinone).
  • a standard sample for example, hydroquinone
  • the concentration in dimethylformamide (dyed charge containing perchloric Sante tiger propyl ammonium Niu arm as a supporting electrolyte of 0. lmo ldm_ 3 is 0. 00 lmo ldm —
  • the value (vs SCE) measured by DC polarography in 3 ) is defined as the oxidation potential of the dye.
  • the value of the oxidation potential (Eox) indicates the ease with which electrons move from the sample to the electrode, and the larger the value (the higher the oxidation potential), the more difficult it is for the electrons to move from the sample to the electrode. In other words, It means that it is hardly oxidized.
  • the dye remaining rate when the area where the reflection density of the status A fill of the printed image is 0.9 to 1.1 in the ozone environment was stored for 24 hours in a 5 ppm ozone environment (reflection density after storage) / Initial concentration X 100) is an index.
  • the dye remaining rate is 60% or more, more preferably 70% or more, and particularly preferably 80% or more, using a dye having an oxidation potential noble than 1.0 V.
  • the residual ratio of the dye when stored for 5 days is preferably at least 25%, more preferably at least 40%, particularly preferably at least 50%.
  • the dye having the above characteristics examples include a phthalocyanine dye (cyan dye) and an azo dye (magenta dye) having specific performance and structure.
  • cyan dye a phthalocyanine dye
  • magenta dye magenta dye
  • the physical properties required of the ink composition, especially the phthalocyanine dye used as an ink jet recording ink, are, in addition to the above-mentioned ozone resistance, excellent in light resistance, and the change in hue and surface state is small (there is less occurrence of bronze, Is difficult to precipitate).
  • xenon light (Xe 1. lW / m (intermittent condition)) was applied to the area where the reflection density 0D of the image printed on the Epson PM photographic paper was 1.0 for 3 days with a TAC filter.
  • Dye residual rate (reflection density after irradiation / initial density X 100) is preferably 90% or more. Further, it is preferable that the dye remaining rate after 14 days is 85% or more.
  • the amount of Cu ion present as a fluorate due to the decomposition of the phthalocyanine dye serves as an index. It is preferable that the equivalent amount of Cu ions present in an actual print be 10 mg / m 2 or less. Cu ion amount you efflux from print, Cu ions in terms of the amount to form a 2 Omg / m 2 or less of the base evening image, after being saved ozone discoloration 24 hours this image 5 ppm of ozone environment, or image It is preferable that the amount of Cu ions flowing out into the water is 20% or less. Before the fading, all Cu compounds are trapped in the image receiving material.
  • Phthalocyanine dyes having the above physical properties 1) increase the oxidation potential
  • the structural feature of the phthalocyanine dye used in the ink composition of the present invention is that the phthalocyanine dye used in the conventional ink is derived from sulfonation of unsubstituted phthalocyanine. In contrast to a mixture whose number and position cannot be specified, a phthalocyanine dye capable of specifying the number and position of substituents is used.
  • the first structural feature is that it is a phthalocyanine dye that does not go through sulfonation of unsubstituted phthalocyanine.
  • the second structural feature is that it has an electron-withdrawing group at the / position of the benzene ring of the furocyanine, and particularly preferably has an electron-withdrawing group at the ⁇ position of every benzene ring. is there.
  • a sulfonyl group Japanese Patent Application No. 2001-47013, Japanese Patent Application No. 2001-192021
  • Japanese Patent Application No. 2001-24352 Japanese Patent Application No.
  • Japanese Patent Application 2001-189982 a heterocyclic sulfamoyl group
  • Japanese Patent Application 2001-96610 Japanese Patent Application 2001-190216
  • those substituted with a heterocyclic sulfonyl group Japanese Patent Application 2001-76689, Japanese Patent Application 2001-190215
  • those substituted with a specific sulfamoyl group Japanese Patent Application 2001-57063
  • those substituted with a carbonyl group Japanese Patent Application No. 2002-012869
  • those having a specific substituent for improving solubility, ink stability, and bronze countermeasures are preferred.
  • Japanese Patent Application No. 2002-012868 Japanese Patent Application No. 2002-012868
  • those made into Li salt Japanese Patent Application No. 2002-012864
  • the first of the physical properties is that it has a high oxidation potential (no less than 1.0 V).
  • the second of the physical characteristics is that it has strong association. Specifically, there are those that specify the association of oil-soluble dyes (Japanese Patent Application No. 2001-64413) and those that specify the association of water-soluble dyes (Japanese Patent Application No. 2001-117350).
  • the introduction of the associative groups tends to cause a decrease in absorbance and shortening of ⁇ ! ⁇ 3 ⁇ even in a dilute solution.
  • the relationship between the number of associative groups and the performance shows that as the number of associative groups increases, the reflection density OD at the same ionic strength decreases. That is, the meeting will proceed on the receiving paper.
  • the relationship between the number of associative groups and the performance is such that the ozone resistance improves as the number of associative groups increases.
  • Dyes having a large number of associative groups tend to improve light fastness.
  • Preferred embodiments of the cyan ink of the present invention using the phthalocyanine dye having the above characteristics are as follows.
  • Xenon light (Xe 1. lW / m (intermittent condition) was applied to a site where the reflection density OD of an image printed on Epson PM photographic receiving paper was 1.0 for 3 days with a TAC filter all day. Cyan ink with 90% or more residual dye.
  • Cyan ink that can penetrate up to 30% or more of the upper part of the image receiving layer of the specific image receiving paper.
  • the phthalocyanine dye contained in the ink composition of the present invention includes the above general formula
  • Phthalocyanine dyes were known as fast dyes, but when used as ink jet recording dyes, they are known to have poor fastness to ozone gas.
  • the phthalocyanine dye in order to reduce the reactivity with ozone, which is an electrophilic agent, the phthalocyanine dye has an oxidation potential nobleer than 1.0 V (vs SCE), thereby improving the robustness to ozone gas. Can be done.
  • the oxidation potential in relation to the structure of the compound, the oxidation potential becomes more noble by introducing an electron-withdrawing group, and becomes lower by introducing an electron-donating group. .
  • the Hammett's substituent constant and P value which are measures of the electron bowing of a substituent and the electron donating property, introduces a substituent having a large p value, such as a sulfinyl group, a sulfonyl group, or a sulfamoyl group.
  • a substituent having a large p value such as a sulfinyl group, a sulfonyl group, or a sulfamoyl group.
  • the phthalocyanine dye having the above oxidation potential is a cyan dye excellent not only in ozone resistance but also in light resistance, and can satisfy the conditions of light resistance and ozone resistance.
  • X 1 x 2 , x 3 and x 4 are each independently: — SO-Zs —S0 2 — Z, Or represents one CO Ri.
  • substituents - SO- Z, - S0 2 -Z, - S0 2 NRiRz and single C ONRiRz are preferred, one S 0 2 - are preferred Z and single S 0 Z NR 1 R 2, - S0 2 — Z is most preferred.
  • any of ai ⁇ a 4 representing the number of substituents represents a number of 2 or more
  • of the Xi ⁇ X 4 which there are two or more may be the same or different to each other V ⁇ , it it And independently represents any of the above groups.
  • x 2 , x 3 and x 4 may each be the same substituent, or Xi, X 2 , X 3 and X 4 may all be —S 0 2 —Z, and Each Z may be a substituent of the same type but partially different from each other, as in the case where different Zs are included, or different substituents such as _S 0 2 —Z and It may contain one S OaN RiRz.
  • Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, Represents a substituted or unsubstituted heterocyclic group.
  • Preferred are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. Of these, a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are most preferred.
  • R 2 is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted Represents a substituted aryl group or a substituted or unsubstituted heterocyclic group.
  • a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group are preferable, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, And substituted heterocyclic groups are more preferred.
  • each of R Xs R 2 is a hydrogen atom.
  • the substituted or unsubstituted alkyl group represented by Ris R 2 and Z is preferably an alkyl group having 1 to 30 carbon atoms.
  • a branched alkyl group is preferred because it enhances the solubility and the stability of the dye, and particularly preferred is a case having an asymmetric carbon (use in a racemic form).
  • substituents, Z described later, R 2, ⁇ ⁇ 2, ⁇ 3 and Upsilon 4 can be mentioned those the same as the substituent in the case where it is possible to have a further substituent.
  • a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they enhance the association of the dye and improve the fastness.
  • it may have a halogen atom or an ionic hydrophilic group.
  • the number of carbon atoms in the alkyl group does not include the carbon atoms in the substituent, and the same applies to other groups.
  • the substituted or unsubstituted cycloalkyl group represented by R 1 R 2 and Z is preferably a cycloalkyl group having 5 to 30 carbon atoms.
  • a case having an asymmetric carbon is particularly preferred because the solubility of the dye and the stability of the ink are increased.
  • substituents include the same substituents as described below when Z, R 2 , Y ls Y 2 , Y 3 and ⁇ 4 can further have a substituent. Among them, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferred because they increase the association of the dye and improve the fastness. In addition, it may have a halogen atom-containing hydrophilic group.
  • the substituted or unsubstituted alkenyl group represented by Ri, R 2 and Z is preferably an alkenyl group having 2 to 30 carbon atoms.
  • a branched alkenyl group is preferable because the solubility of the dye is improved, and a case having an asymmetric carbon (use in a racemic form) is particularly preferable.
  • the substituent include the same substituents as described below when Z, RR 2 , Y t , Y 2 , ⁇ 3 and ⁇ 4 can further have a substituent.
  • a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they increase the association of the dye and improve the fastness.
  • it may have a halogen atom or an ionic hydrophilic group.
  • the substituted or unsubstituted aralkyl group represented by R ls R 2 and Z is preferably an aralkyl group having 7 to 30 carbon atoms.
  • a branched aralkyl group is preferable, because it enhances the solubility of the dye and the stability of the ink, and particularly, a case having an asymmetric carbon (use in a racemic form) is particularly preferable.
  • the substituent include the same substituents as described below when Z, R 1N R 2 , Yj, Y 2 , Y 3 and Y 4 can further have a substituent.
  • a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they increase the association of the dye and improve the fastness.
  • it may have a halogen atom or an ionic hydrophilic group.
  • the substituted or unsubstituted aryl group represented by R 2 and Z is preferably an aryl group having 6 to 30 carbon atoms.
  • substituents, Z described later, R ls R 2, Yi, Y 2, Y 3 and Y 4 are as same as the substituent in the case where each may further have a substituent group.
  • an electron-withdrawing group is particularly preferable because the oxidation potential of the dye is noble and the fastness is improved.
  • the electron withdrawing group Hammett's substituent constant And those with positive p-values.
  • a halogen atom, a heterocyclic group, a cyano group, a carboxyl group, an acylamino group, a sulfonamide group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imido group, an acyl group, a sulfo group, and a quaternary ammonium group are preferable.
  • a cyano group More preferred are a cyano group, a carboxyl group, a sulfamoyl group, a sulfamoyl group, a sulfonyl group, an imido group, an acyl group, a sulfo group and a quaternary ammonium group.
  • the heterocyclic group represented by R 1 R 2 and Z is preferably a 5- or 6-membered ring, which may be further condensed. Further, it may be an aromatic hetero ring or a non-aromatic hetero ring.
  • the heterocyclic groups represented by R 2 and Z are exemplified in the form of a heterocyclic ring by omitting the substitution position.
  • the substitution position is not limited. It is possible to substitute at positions 3, 3 and 4.
  • an aromatic heterocyclic group is preferable, and preferable examples thereof are the same as those described above.
  • examples thereof include pyridine, pyrazine, pyrimidine, pyridazine, triazine, virazol, imidazole, benzimidazole, triazole, thiazole, and benzothiazo.
  • They may have a substituent, and examples of the substituent include those described below where Z, R 1 R 2 , Y ls Y 2 , Y 3 and ⁇ 4 can further have a substituent.
  • the same substituents can be mentioned.
  • Preferred substituents are the same as those of the aryl group, and more preferred substituents are the same as the more preferred substituents of the aryl group.
  • Yis ⁇ 2 , ⁇ 3 and ⁇ 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group.
  • a hydrogen atom, a halogen atom, a cyano group, a carboxyl group and a sulfo group are preferred, and a hydrogen atom is most preferred.
  • R ls R 2 , Yi, Y 2 , Y 3 and Y 4 are groups capable of further having a substituent, they may further have the following substituents.
  • Specific examples of each of the above groups for example, methyl, ethyl, propyl, isopropyl, sec- Butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropy
  • N N-dipropylsulfamoylamino
  • alkylthio group for example, methylthio, octylthio, 2-phenyloxyl
  • alkyloxycarbonylamino group eg, methoxycarbonylamino
  • a sulfonamide group eg, methane Sulfonamide, benzenesulfonamide, p-toluenesulfonamide
  • sulfamoyl group for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl
  • sulfamoyl group for example, N-ethyls
  • sulfonyl group for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenes
  • the phthalocyanine dye represented by the general formula (C-I) When the phthalocyanine dye represented by the general formula (C-I) is water-soluble, it preferably has an ionic hydrophilic group.
  • the ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group, and the like.
  • a carboxyl group, a phosphono group and a sulfo group are preferred, and a carboxyl group and a sulfo group are particularly preferred.
  • the carboxyl, phosphono and sulfo groups may be in the form of a salt
  • examples of the counter ion which forms a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic compound. Cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium ion) are included.
  • alkali metal salts are preferred, and lithium salts are particularly preferred because they enhance the solubility of the dye and improve the stability of the ink.
  • the number of ionic hydrophilic groups is preferably at least two per molecule of the phthalocyanine dye, and particularly preferably at least two sulfo groups and / or carboxyl groups.
  • Ai ⁇ a 4 each independently represents an integer of 0 to 4, not the this all are not 0 at the same time.
  • bib independently represents an integer from 0 to 4. Note that when either Ai ⁇ a 4 and ⁇ of is an integer of 2 or more, either Xi ⁇ X 4 and Yi ⁇ Y 4 will be present a plurality, even they be the same or different Good. a and satisfy the relationship Particularly preferred are combinations in which represents 1 or 2, and represents 3 or 2, and among them, the combination in which a represents 1 and represents 3 is most preferred.
  • M represents a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof.
  • Preferred as M are, in addition to a hydrogen atom, metal elements such as Li, Na, K, M :, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni ⁇ Ru, Rh s Pd, Os, Ir, Pt, Cxi, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi Can be VO, GeO, and the like are preferable examples of the oxidizing agent.
  • Preferred examples of the hydroxide include Si (OH) 2 , Cr (OH) 2 , and Sn (OH) 2 .
  • the halides A1C1, SiCl 2, VC1, VC1 2, VOCl, FeCl, GaCl, Zr CI , and the like.
  • Cu, Ni, Zn, Al and the like are preferable, and Cu is most preferable.
  • Pc phthalocyanine ring
  • Pc-M-LM-Pc dimer
  • L a divalent linking group
  • M at that time may be a dimer. They may be the same or different.
  • a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are preferable. Is more preferably a compound in which all the substituents are the above-mentioned preferred groups.
  • a phthalocyanine dye having a structure represented by (C-II) is more preferable.
  • the phthalocyanine dye represented by formula (C-II) of the present invention will be described in detail.
  • X U to X 14 and Y U to Y 18 have the same meanings as Xi to X 4 and Y YA in the general formula (C-I), and preferred examples are also the same. It is. M has the same meaning as M in the general formula (C-I), and preferred examples are also the same.
  • X u , X 12 , X 13 and X 14 may each be exactly the same substituent, or for example X !, X 2 , X 3 and X 4 are all —S 0 2 —Z , And each Z is the same type of substituent, but partially different, as in the case where they include different ones. / May be different from each other, or different substituents may be included, for example, one of S 0 2 —Z and —S OzN RiRg.
  • phthalocyanine dyes represented by the general formula (C-II) particularly preferred combinations of the substituents are as follows.
  • Z is each independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted Heterocyclic groups are most preferred.
  • a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group is present in the substituent, because the association property is improved and the robustness is improved.
  • Rj and R 2 are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group And a substituted aryl group and a substituted heterocyclic group are more preferred.
  • both R 2 are hydrogen atoms.
  • the substituent has an asymmetric carbon (use in a racemic form)
  • a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group is present in the substituent, because the association property is improved and the robustness is improved.
  • Y U to Y 18 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a aryl group, a cyano group, an alkoxy group, an amide group, a perido group, a sulfonamide group, Preferred are a rubamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group, particularly a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, or a sulfo group, and most preferably a hydrogen atom. I like it.
  • a u ⁇ a 14 are therewith it independently, preferably 1 or 2, and particularly preferably all are 1.
  • M represents a hydrogen atom, a metal element or an oxide, a hydroxide, or a halide thereof, particularly preferably Cu, Ni, Zn, and A1, and particularly preferably Cu.
  • the phthalocyanine dye represented by the general formula (C- ⁇ ) When the phthalocyanine dye represented by the general formula (C- ⁇ ) is water-soluble, it preferably has an ionic hydrophilic group.
  • the ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group, and the like.
  • a carboxyl group, a phosphono group and a sulfo group are preferred, and a carboxyl group and a sulfo group are particularly preferred.
  • the carboxyl, phosphono, and sulfo groups may be in the form of a salt, and examples of counter ions that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic compound. Cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are included.
  • alkali metal salts are preferred, and lithium salts are particularly preferred because they enhance the solubility of the dye and improve the stability of the ink.
  • the number of ionic hydrophilic groups is preferably at least two in one molecule of the phthalocyanine dye, and particularly preferably at least two sulfo groups and Z or carboxyl groups.
  • a compound in which at least one of various substituents is the above-mentioned preferable group is preferable, and more various substituents are preferable. Is more preferably a compound in which all the substituents are the above-mentioned preferred groups.
  • the chemical structure of the phthalocyanine dye of the present invention includes an electron-withdrawing group such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group, and each of the four phthalocyanine groups. It is preferred to introduce at least one of the substituents on the entire phthalocyanine skeleton into the benzene ring at a total of 1.6 or more in total.
  • the Hammett's substituent constant crp value will be described briefly.
  • the Hammett's rule is an empirical rule proposed by LP Hamme tt in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, but it is widely accepted today. .
  • the substituent constants determined by Hammett's rule include crp values and crm values, and these values can be found in many general books. For example, see JA Dean, “Ijange's Handbook of C. nem ⁇ stry ”, 12th edition, 1979 ( ⁇ .Graw-Hi11) and special edition of“ Chemistry ”, No. 122, 96-; L03, 1979 (Nankodo).
  • each substituent is limited or explained by Hammett's substituent constant and p, but this is limited to only those substituents having a known value in the literature, which can be found in the above-mentioned books. It does not mean that even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on the Hammett rule.
  • the compounds of the present invention include compounds that are not benzene derivatives, the rp value is used as a measure of the electronic effect of the substituent, regardless of the substitution position. In the present invention, the crp value is used in this sense.
  • the mixture is a mixture of analogs having different introduced numbers. Therefore, the general formula often represents the mixture of these analogs statistically averaged.
  • the phthalocyanine-based dye analog mixture represented by the general formula (C-I) or (C-II) is defined by classifying the mixture into the following three types based on the substitution position.
  • 5-substituted type a phthalocyanine dye having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position.
  • Hy-substitution type 1 and / or 4, 5 and / or 8, 9 and also Is a phthalocyanine dye having a specific substituent at position 12, 13 and / or 16
  • a, ⁇ -position mixed substitution type a phthalocyanine dye having a specific substituent at positions 1 to 16 without regularity
  • phthalocyanine derivatives used in the present invention are, for example, co-authored by Ichiko Shirai, "Phthalocyanine-Chemistry and Function 1" (P. 1-62), published by Ibiichi Co., Ltd .; 'Phthal oc yanines— Propert les and Appl i cat i ons'
  • the phthalocyanine compounds represented by the general formula (C-I) of the present invention include WO00 / 17275, WO00 / 08103, WO00 / 08101, WO98 / 41853, and JP-A-10-36471.
  • the compound can be synthesized through a sulfonation, sulfonyl chloride, or amidation reaction of an unsubstituted phthalocyanine compound.
  • sulfonation can occur at any position of the phthalocyanine nucleus, and it is difficult to control the number of sulfonated.
  • the phthalocyanine compound represented by the general formula (C-II) of the present invention is, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindrin derivative (compound Q) represented by the following formula represented by the general formula (M). Or a 4-sulfofurononitrile derivative (compound R) represented by the following formula:
  • X p corresponds to x u , x 12 , x 13 or x 14 in the above general formula (C-II).
  • Y q, Y q is that it it the general formula (C one II) in the Y u, ⁇ 12, ⁇ 13 , ⁇ 14, ⁇ 15, ⁇ 6, corresponding to Upsilon 17 or Upsilon 18.
  • M ′ represents a cation. Examples of the cation represented by M ′ include an alkali metal ion such as Li, Na, and K, and an organic cation such as trietium / ammonium ion and pyridinium ion.
  • M has the same meaning as M in the above general formulas (C-I) and (C-II), and Y is a monovalent or halogen atom, an acetate anion, acetylacetonate, oxygen or the like. Represents a divalent ligand, and d is an integer of 1 to 4.
  • the above synthesis method a desired number of substituents can be introduced.
  • the above synthesis method is used for synthesizing the phthalocyanine compound of the general formula (C-I). This is extremely superior to the method already described.
  • the phthalocyanine compound represented by the general formula (C-—) thus obtained is generally represented by the following general formulas (a) — 1 to (a) — 4 which are isomers at each substitution position of X p It is a mixture of compounds, that is, a ⁇ -substituted type.
  • the phthalocyanine dye represented by the general formula (C-I) can be synthesized according to the above-mentioned patent.
  • the phthalocyanine dyes represented by the general formula (C-II) can be prepared by the methods described in JP-A-2001-226275, JP-A-2001-96610, JP-A-2001-47013, and 2001- It can be synthesized by the method described in each publication of 193638. Further, the starting materials, dye intermediates and synthetic routes are not limited to these.
  • the azo dye used in the ink composition of the present invention is a dye having an absorption maximum in a spectral region of 500 to 58 Onm in an aqueous medium, and having a noble oxidation potential higher than 1.0 V (vsSCE). That is the basic feature.
  • the complex A and the heterocycle B may have the same structure.
  • the heterocycle A and the heterocycle B are specifically a 5-membered or 6-membered heterocycle, selected from pyrazole, imidazole, triazole, oxazole, thiazole, selenazole, pyridone, pyrazine, pyrimidine, and pyridine. Is complex. Specifically, Japanese Patent Application 2000-15
  • the second of the preferred structural features of the azo dye is that the azo group is an azo dye in which at least one of the azo dyes is directly bonded to an aromatic nitrogen-containing 6-membered heterocyclic ring as a power coupling component.
  • the auxochrome has the structure of an aromatic ring amino group or a heteroamino group, specifically, an anilino group or a heteroarylamino group.
  • the fourth of the preferred structural features is to have a three-dimensional structure. Specifically, it is described in Japanese Patent Application No. 2002-12015.
  • the oxidation potential of the dye can be increased, and the ozone resistance can be improved.
  • Means for increasing the oxidation potential include removing hydrogen from the azo dye.
  • the azo dye of the general formula (M-I) is particularly preferred. The means for increasing the oxidation potential of the azo dye is specifically described in Japanese Patent Application No. 2001-254878.
  • the (maximum absorption wavelength) is 500 to 580 nm, and it is preferable that the half-width at the long wavelength side and the short wavelength side of the maximum absorption wavelength is small, that is, sharp absorption is obtained. Specifically, it is described in JP-A-2002-309133.
  • the azo dye of the general formula (M-I) is used, a sharp absorption can be realized by introducing a methyl group at the position.
  • the compound represented by formula (M-I), which is an azo dye preferably used in the present invention, will be described below.
  • A represents a 5-membered heterocyclic group.
  • R 5 and R 6 each independently represent a hydrogen atom or a substituent, and the substituent is an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Represents a rubamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and a hydrogen atom of each of the substituents may be substituted.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and the substituent is a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group , An alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, an acyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterodioxy group, a silyloxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group Group, aryloxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, aryl Monosul
  • R 1 and R 5 , or R 5 and R 6 may combine to form a 5- to 6-membered ring.
  • A represents a 5-membered heterocyclic group, and examples of heteroatoms in the heterocyclic ring include N, ⁇ , and S.
  • Preferred is a nitrogen-containing 5-membered heterocyclic ring, which may be condensed with an aliphatic ring, an aromatic ring, or another heterocyclic ring.
  • Preferred examples of the heterocyclic ring for A include a pyrazole ring, an imidazole ring, a thiazolyl ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring and a benzoisothiazole ring.
  • Each heterocyclic group may further have a substituent.
  • a pyrazoyl ring an imidazole ring, an isothiazole ring, a thiadiazole ring, and a benzothiazole, which are represented by the following general formulas (a) to (:), are preferable.
  • R 7 to R 2Q represent the same substituents as G and R ⁇ R 2 in the general formula (M-I).
  • a pyrazole ring and an isothiazole ring represented by the general formulas (a) and (b), and most preferred is represented by the general formula (a) It is a biazo ring.
  • R 5 and R 6 each independently represent a hydrogen atom or a substituent, and the substituent is an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group Represents an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and the hydrogen atom of each of the substituents may be substituted.
  • R 5 and R 6 preferably include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group. More preferably, they are a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or an arylsulfonyl group. Most preferred are a hydrogen atom, an aryl group and a heterocyclic group. Said each substitution
  • R 5 and R 6 are not hydrogen atoms at the same time.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and the substituent is a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group Group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acryl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acryloxy group, alkamoyloxy group, alkoxy Carbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, Arylsulfonylamino, heterosulfonylamino, nitro An
  • G represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group, an amino group, an acylamino group, an ureido group, or a sulfamoylamino group.
  • alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group or a heterocyclic thio group more preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, It is an acyloxy group, an amino group or an acylamino group, among which a hydrogen atom, an amino group (preferably an anilino group) and an acylamino group are most preferred.
  • the hydrogen atom of each of the substituents may be substituted.
  • R ⁇ R 2 there may be mentioned a hydrogen atom, an alkyl group, a halogen atom, alkoxide aryloxycarbonyl group, a carboxyl group, a force Rubamoiru group, hydroxy group, alkoxy group, a Shiano group.
  • the hydrogen atom of each of the substituents may be substituted.
  • R 1 and R 5 , or R 5 and R 6 may combine to form a 5- to 6-membered ring.
  • the azo dye represented by the general formula (M-I) When the azo dye represented by the general formula (M-I) is a water-soluble dye, it must further have an ionic hydrophilic group as a substituent at any position on A, RRR ⁇ R ⁇ G. Is preferred.
  • the ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group, and the like.
  • a carboxyl group, a phosphono group and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable.
  • the carboxyl, phosphono and sulfo groups may be in the form of a salt, and examples of the counter ion forming a salt include an ammonium ion, an alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and an organic ion. Contains cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium ion).
  • halogen atom examples include a fluorine atom, a chlorine atom and a bromine atom.
  • the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group.
  • the hydrogen atoms present in such "alkyl group” indicate that they are being substituted by an substituent groups listed above G, RR 2.
  • the aliphatic group may have a branch or may form a ring.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms.
  • the aryl part of the aralkyl group and the substituted aralkyl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.
  • Examples of the aliphatic group include a methyl group, an ethyl group, a butyl group, an isopropyl group, a t-butyl group, a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group,
  • Examples thereof include a monosulfopropyl group, a 4-sulfobutyl group, a cyclohexyl group, a benzyl group, a 2-phenethyl group, a vinyl group, and an aryl group.
  • Aromatic groups refer to aryl and substituted aryl groups.
  • the aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.
  • the aromatic group preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms.
  • aromatic group examples include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group and an m- (3-sulfopropylamino) phenyl group.
  • the heterocyclic group includes a substituted heterocyclic group.
  • the heterocyclic group may have a heterocyclic ring fused with an aliphatic ring, an aromatic ring or another heterocyclic ring.
  • the heterocyclic group is preferably a 5- or 6-membered heterocyclic group.
  • the substituent include an aliphatic group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a sulfamoyl group, and an ionic hydrophilic group.
  • Examples of the complex ring group include a 2-pyridyl group, a 2-phenyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a 2-benzoxazolyl group, and a 2-furyl group.
  • the rubamoyl group includes a substituent rubamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
  • the alkoxycarbonyl group includes a substituted alkoxycarbonyl group.
  • the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.
  • Examples of the substituent include an ionic hydrophilic group.
  • Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
  • the aryloxycarbonyl group includes a substituted aryloxycarbonyl group.
  • the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms.
  • Examples of the substituent include an ionic hydrophilic group.
  • Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
  • the heterocyclic oxycarbonyl group includes a substituted heterodioxycarbonyl group.
  • the heterocyclic group include the heterocyclic rings described in the above heterocyclic group.
  • a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms is preferable.
  • the substituent include an ionic hydrophilic group.
  • the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group.
  • the acyl group includes a substituted acyl group.
  • the acyl group is preferably an acyl group having 1 to 20 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • Examples of the acetyl group include an acetyl group and a benzoyl group.
  • the alkoxy group includes a substituted alkoxy group.
  • the alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms.
  • Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group and a 3-carboxypropoxy group.
  • the aryloxy group includes a substituted aryloxy group.
  • the aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms.
  • the substituent include an alkoxy group and an ionic hydrophilic group.
  • Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group and an o-methoxyphenoxy group.
  • the heterocyclic oxy group includes a substituted heterodioxy group.
  • the heterocyclic ring include the heterocyclic rings described in the above heterocyclic group.
  • the heterooxy group a heterocyclic group having 2 to 20 carbon atoms is preferable.
  • the substituent include an alkyl group, an alkoxy group, and an ionic hydrophilic group.
  • the heterocyclic oxy group include a 3-pyridyloxy group and a 3-chenyloxy group.
  • silyloxy group an aliphatic group having 1 to 20 carbon atoms and a silyloxy group substituted with an aromatic group are preferable.
  • examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.
  • the acyloxy group includes a substituted acyloxy group.
  • the acyloxy group is preferably an alkoxy group having 1 to 20 carbon atoms.
  • Examples of the substituent include an ionic hydrophilic group.
  • Examples of the above-mentioned acyloxy group include an acetyloxy group and
  • the rubamoyloxy group includes a substituent rubamoyloxy group.
  • the substituent include an alkyl group.
  • Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.
  • the alkoxycarbonyloxy group includes a substituted alkoxycarbonyloxy group.
  • the alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 20 carbon atoms.
  • Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.
  • the aryloxycarbonyloxy group includes a substituted aryloxycarbonyloxy group.
  • the aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms.
  • Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.
  • Amino groups include substituted amino groups.
  • Examples of the substituent include an alkyl group, a aryl group and a heterocyclic group, and the alkyl group, aryl group and heterocyclic group may further have a substituent.
  • the alkylamino group includes a substituted alkylamino group. As the alkylamino group, an alkylamino group having 1 to 20 carbon atoms is preferable.
  • Examples of the substituent include an ionic hydrophilic group.
  • Examples of the alkylamino group include a methylamino group and a getylamino group.
  • the arylamino group includes a substituted arylamino group.
  • the arylamino group is preferably an arylamino group having 6 to 20 carbon atoms.
  • the substituent include a halogen atom and an ionic hydrophilic group.
  • Examples of the arylamino group include a phenylamino group and a 2-chlorophenylamino group.
  • the heterodiamino group includes a substituted heterodiamino group.
  • the heterocyclic ring include the heterocyclic groups described in the above heterocyclic group.
  • the heterocyclic amino group is preferably a heterocyclic amino group having 2 to 20 carbon atoms.
  • the substituent include an alkyl group, a halogen atom, and an ionic hydrophilic group.
  • the acylamino group includes a substituted amino group.
  • an acylamino group having 2 to 20 carbon atoms is preferable.
  • the substituent include an ionic hydrophilic group.
  • the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino and a 3,5-disulfopenzylamino group.
  • Perido groups include substituted ureido groups.
  • the ureido group is preferably a paraido group having 1 to 20 carbon atoms.
  • Examples of the substituent include an alkyl group and an aryl group.
  • Examples of the Ureido groups are 3- Mechiruurei de group, 3, 3-dimethylcarbamoyl Honoré ⁇ raid group, and a 3 Fueniruurei de group 9
  • the sulfamoylamino group includes a substituted sulfamoylamino group.
  • substituent include an alkyl group.
  • sulfamoylamino group include an N, N-dipropylsulfamoylamino group.
  • the alkoxycarbonylamino group includes a substituted alkoxycarbonylamino group.
  • the alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms.
  • Examples of the substituent include an ionic hydrophilic group.
  • Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.
  • the aryloxycarbonylamino group includes a substituted aryloxycarbonylamino group.
  • the aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms.
  • Examples of the substituent include an ionic hydrophilic group.
  • Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.
  • the alkylsulfonylamino group and the arylsulfonylamino group include a substituted alkylsulfonylamino group and a substituted arylsulfonylamino group.
  • the alkylsulfonylamino group and arylsulfonylamino group are preferably an alkylsulfonylamino group and an arylsulfonylamino group having 1 to 20 carbon atoms.
  • the examples of the above three substituents include an ionic hydrophilic group.
  • alkyl sulfonylamino group and arylsulfonylamino group examples include a methylsulfonylamino group, an N-phenylmethylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino group. Includes mino groups.
  • the heterocyclic sulfonylamino group includes a substituted heterocyclic sulfonylamino group.
  • the heterocyclic group include the heterocyclic groups described in the above heterocyclic group.
  • the heterosulfonylamino group is preferably a heterosulfonylamino group having 1 to 12 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • the heterocyclic sulfonylamino groups include a 2-phenylsulfonylamino group and a 3-pyridylsulfonylamino group.
  • the alkylthio group, arylthio group and heterocyclic thio group include a substituted alkylthio group, a substituted arylthio group and a substituted heterocyclic thio group.
  • Examples of the heterocyclic group include the heterocyclic rings described in the above-mentioned heterocyclic group.
  • the alkylthio group, arylthio group and heterocyclic thio group preferably have 1 to 20 carbon atoms.
  • Examples of the substituent include an ionic hydrophilic group.
  • Examples of the alkylthio group, arylthio group and heterocyclic thio group include a methylthio group, a phenylthio group and a 2-pyridylthio group.
  • the alkylsulfonyl group and the arylsulfonyl group include a substituted alkylsulfonyl group and a substituted arylsulfonyl group.
  • Examples of the alkylsulfonyl group and the arylsulfonyl group include a methylsulfonyl group and a phenylsulfonyl group, respectively.
  • the heterosulfonyl group includes a substituted heterosulfonyl group.
  • the heterocyclic ring include the heterocyclic rings described in the above heterocyclic group.
  • the heterocyclic sulfonyl group is preferably a heterosulfonyl group having 1 to 20 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • the heterocyclic sulfonyl group include a 2-phenylsulfonyl group and a 3-pyridylsulfonyl group.
  • alkylsulfinyl group and the arylsulfinyl group include a substituted alkylsulfinyl group and a substituted arylsulfinyl group.
  • alkylsulfinyl and arylsulfinyl groups include methylsulfinyl and phenylsulfinyl, respectively.
  • the heterocyclic sulfinyl group includes a substituted heterocyclic sulfinyl group.
  • Examples of the heterocyclic ring include the heterocyclic rings described in the above heterocyclic group.
  • the heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having 1 to 20 carbon atoms.
  • Examples of the group include an ionic hydrophilic group.
  • Examples of the heterosulfinyl group include:
  • the sulfamoyl group includes a substituted sulfamoyl group.
  • the substituent include an alkyl group.
  • Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di (2-hydroxyethyl) sulfamoyl group.
  • M_I a particularly preferred structure is represented by the following general formula (M-Ia).
  • R 3 and R 4 each independently represent a hydrogen atom or a substituent, and the substituent is an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group Represents an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group.
  • a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group is preferred, and a hydrogen atom, an aromatic group and a heterocyclic group are particularly preferred.
  • Z 1 represents an electron-withdrawing group having a Hammett's substituent constant and a p-value of 0.20 or more.
  • Z 1 is preferably an electron-withdrawing group having a crp value of 0.30 or more, more preferably 0.45 or more, and particularly preferably 0.60 or more. It is desirable not to exceed 0.
  • the electron-absorbing I groups having a Hammett substituent constant and a p-value of 0.60 or more include a cyano group, a nitro group, an alkylsulfonyl group (eg, a methylsulfonyl group, an arylsulfonyl group (eg, phenyl) Sulfonyl group) as an example.
  • Examples of the electron-withdrawing group having a p-value of 0.45 or more include an acyl group in addition to the above.
  • alkoxycarbonyl group eg, dodecyloxycarbonyl group
  • aryloxycarbonyl group eg, m-chlorophenoxycarbonyl
  • alkylsulfinyl group eg, n-propylsulfinyl
  • Examples include a arylsulfinyl group (eg, phenylsulfinyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), and a halogenated alkyl group (eg, trifluoromethyl).
  • Examples of the electron-withdrawing group having a Hammett substituent constant and a p-value of 0.30 or more include, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N— Dibutylcarbamoyl), halogenated alkoxy group (for example, trifluoromethyloxy), halogenated aryloxy group (for example, pentafluorophenyloxy), sulfonyloxy group (for example, methylsulfonyloxy group), halogen Alkylthio groups (eg, difluoromethylthio), aryl groups substituted with two or more electron-withdrawing groups having a crp value of 0.15 or more (eg, 2,4-dinitrophenyl, Phenyl), and heterocycles (eg, 2-benzoxazolyl, 2-benzothiazolyl, 1-pheny
  • the electron-absorbing I-group having a crp value of 0.20 or more include a halogen atom in addition to the above.
  • an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and a 6 to 20 carbon atoms Preferred are an arylsulfonyl group, a C1 to C20 halobamoyl group and a C1 to C20 halogenated alkyl group. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.
  • Z 2 represents a hydrogen atom or a substituent, and the substituent represents an aliphatic group, an aromatic group, or a heterocyclic group.
  • Z 2 is preferably an aliphatic group, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • Q represents a hydrogen atom or a substituent, and the substituent represents an aliphatic group, an aromatic group, or a complex group. Among them, Q is derived from the nonmetallic atoms necessary to form 5 to 8 members
  • the 5- to 8-membered group may be substituted or may be a saturated ring or have an unsaturated bond.
  • an aromatic group and a heterocyclic group are particularly preferred.
  • Preferred non-metallic atoms include a nitrogen atom, an oxygen atom, a zeolite atom or a carbon atom.
  • Such a structure include, for example, a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a pyridine, a pyrimidine ring, a pyrazine ring, a pyridazine ring, Examples thereof include a triazine ring, an imidazole ring, a benzimidazole ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an oxane, a sulfolane ring and a thiane ring.
  • each substituent described in the general formula (M-Ia) may be substituted.
  • substituents described in (M- I), G include the groups exemplified or an ionic hydrophilic group RK R 2.
  • R 5 and R 6 are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group.
  • R 5 and R 6 are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group.
  • An aryl group more preferably a hydrogen atom, an aryl group, a heterocyclic group, or a sulfonyl group, and most preferably a hydrogen atom, an aryl group, or a heterocyclic group.
  • R 5 and R 6 are not both hydrogen atoms.
  • G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group, or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group, or an acylamino group, and most preferably a hydrogen atom or an amino group.
  • an acylamino group is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group, or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group, or an acylamino group, and most preferably a hydrogen atom or an amino group.
  • an acylamino group is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group, or an acylamino group, more preferably a hydrogen atom, a halogen atom, an
  • a pyrazole, an imidazole, an isothiazole ring, a thiadiazol ring, and a benzothiazole ring are preferable, and further a birazol ring and an isothiazole ring are most preferable. It is a ring.
  • a compound in which at least one of various substituents is the above-mentioned preferable group is preferable.
  • the substituents are the aforementioned preferred groups, and most preferably the compounds wherein all the substituents are the aforementioned preferred groups.
  • azo dye represented by the general formula (M-I) are shown below, but the azo dye used in the present invention is not limited to the following examples.
  • the amount of the dye contained in the ink composition of the present invention is preferably at least 0.1% by mass, more preferably at least 0.5% by mass.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
  • the ink composition of the present invention contains a dye, a surfactant, and, if necessary, other additives appropriately selected.
  • the dye contained in the ink composition acts as a dye, a colorant, and the like on a recording material.
  • the ink composition is preferably used as a coloring composition for image formation such as an ink paint, and is particularly useful as an ink for ink jet recording which is excellent in ejection stability at the time of recording and image storability of a recorded image. .
  • the ink composition of the present invention other dyes may be used together with the dye of the present invention in order to adjust the color tone for obtaining a full-color image.
  • dyes that can be used in combination, the dyes described in paragraphs (001) to (0884) of JP-A-2001-26209 are used. it can.
  • Examples of other dyes that can be used in combination include the following.
  • Examples of yellow dyes include, for example, aryl or heteroaryl azo dyes having phenols, naphtholes, anilines, pyrazolones, pyridones, and open-chain active methylene compounds as power coupling components; Azomethine dyes having chain-type active methylene compounds; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; Examples of the dye species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.
  • the count cation may be an alkali metal or an inorganic cation such as ammonium.
  • organic cations such as pyridinium and quaternary ammonium salts, and polymer cations having them in the partial structure.
  • magenta dyes for example, aryl or hetarylazo dyes having phenols, naphtholes, anilines as coupling components;
  • Azomethine dyes having pyrazones and pyrazotriazoles as ring components methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes; diphenylmethane dyes, triphenylmethane dyes, and xanthen dyes
  • carbon dyes include, for example, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.
  • These dyes may exhibit a magenta color only when a part of the chromophore dissociates, and in that case, the count thione is an inorganic cation such as an alkali metal or ammonium.
  • organic cations such as pyridinium and quaternary ammonium salts may be used, and further, polymer cations having these in a partial structure may be used.
  • cyan dyes examples include azomethine dyes such as indoor diphosphorine dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; and carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye.
  • These dyes may exhibit cyanide only when a part of the chromophore is dissociated, and in that case, the cation may be an inorganic metal cation such as alkali metal or ammonium.
  • organic cations such as pyridinium and quaternary ammonium salts may be used, and further, polymer cations having these in a partial structure may be used.
  • a black dye such as a polyazo dye can be used.
  • water-soluble dyes such as direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes.
  • direct dyes such as direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes.
  • Thick biorate 1 I, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48
  • a pigment may be used in combination with the ink composition of the present invention.
  • pigment used in the present invention commercially available pigments and known pigments described in various documents can be used.
  • Color Index The Society of Dyers and Colorists
  • Revised New Pigment Handbook Japan Pigment Technology Association (1989)
  • Longtest Pigment Application Technology CMC Publishing (1986)
  • Print Ink Technology Published in CMC (1984)
  • Industrial Organic Pigments VH Verlassgesellschaft, 1993
  • organic pigments include azo pigments (azo lake pigments, insoluble azo pigments, condensed azo pigments, chelating azo pigments), and polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, Indigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, diketovirolopyrrole pigments, etc.), dyeing lake pigments (acid or basic dye lake pigments), azine pigments, etc.
  • azo pigments azo lake pigments, insoluble azo pigments, condensed azo pigments, chelating azo pigments
  • polycyclic pigments phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, Indigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, diket
  • Inorganic pigments include yellow pigments such as CI Pigment Yellow 34, 37, 42 and 53, red pigments such as CI Pigment Red 101 and 108, and blue pigments such as CI Pigment Blue 27, 29, 17: 1, and black pigments. Pigments such as CI Pigment Black 7, magnetite, and white pigments such as I. Pigment White 4, 6, 18, and 21.
  • Preferable pigments having a color tone for image formation include phthalocyanine pigments for blue or cyan pigments, anthraquinone-based indanthrone pigments (for example, CI Pigment Blue 60, etc.), and dye lake pigment-based triarylcarboneme.
  • Phthalocyanine pigments preferably, copper phthalocyanine such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, etc.
  • copper phthalocyanine and aluminum phthalocyanine pigments described in European Patent No. 860475, metal-free phthalocyanine which is CI Pigment Blue 16, phthalocyanine whose central metal is Zn, Ni, Ti, etc. are preferably CI.
  • Pigment Blue 15: 3, 15: 4, and aluminum phthalocyanine are the most preferred.
  • azo pigments for the red or purple pigments, azo pigments (preferred examples include CI Pigment Red 3, 5, 11, 22, 38, 48: 1, 48: 2, 48: 3, 48: 3, 48 : 4, 49: 1, 52: 1, 53: 1, 57: 1, 63: 2, 144, 146, 184), among which CI Pigment Red 57: 1, 146, 184), quinacridone pigments (preferred examples are I. Pigment Red 122, 192, 202, 207, 209, CI Pigment Violet 19, 42, and particularly preferred are CI Pigment Red 122) Dyeing lake pigment triarylcarbonate pigment
  • xanthene-based CI Pigment Red 81: 1, CI Pigment Violet 1, 2, 3, 27 and 39 dioxazine-based pigments (for example, I. Pigment Violet 23 and 37), Pigments (for example, CI Pigment Red 254), perylene pigments (for example, I. Pigment Violet 29), anthraquinone pigments (for example, I. Pigment Violet 5: 1, 31, 31 and 33), and thioindigo (for example, CI Pigment).
  • Red 38 and 88 are preferably used.
  • azo pigments As yellow pigments, azo pigments (preferred examples are monoazo pigment-based I. Pigment Yello 1, 3, 74, 98, and disazo pigment-based I. Pigment Yello 12, 13, 14, 16, 17, 83; Among these, benzo-based CI Pigment Yellow 93, 94, 95, 128, 155, and penzimidazolone-based I. Pigment Yellow 120, 151, 154, 156, 180, etc. ), Isoindrin isoidrinone pigments (preferred examples include CI Pigment Yellow 109, 110, 137, 139), quinophthalone pigments (preferred examples include CI Pigment Yellow 138), and flapantron pigments (eg, I. Pigment Yellow 24) is preferably used.
  • the black pigment include inorganic pigments (preferably, for example, carbon black and magnetite) and aniline black.
  • orange pigments such as CI Pigment Orange 13, 16
  • pigments such as CI Pigment Green 7
  • the pigment that can be used in the present technology may be the above-described naked pigment, or may be a surface-treated pigment.
  • Surface treatment methods include a method of surface coating with a resin or wax, a method of attaching a surfactant, and reactive substances (for example, radicals generated from silane coupling agents, epoxy compounds, polyisocyanates, and diazonium salts). And the like can be attached to the pigment surface, and this is described in the following literature and patents.
  • the pigment may be further dispersed using a dispersant.
  • a dispersant various known dispersants can be used in accordance with the pigment to be used, for example, a surfactant-type low-molecular-weight dispersant or a polymer-type dispersant. Examples of the dispersant include those described in JP-A-3-69949, EP 549486 and the like.
  • a pigment derivative called a synergist may be added to promote the adsorption of the dispersant to the pigment.
  • the particle size of the pigment which can be used in the present invention is preferably in the range of 0.01 to: L 0 // after dispersion, more preferably 0.05 to 1 //.
  • a known dispersion technique used in the production of ink or toner can be used.
  • Attritors colloid mills, ball mills, three-hole mills, pearl mills, super mills, impellers, desperers, KD mills, dynatrons, and pressure kneaders. Details are described in “Latest Pigment Application Technology” (CMC Publishing, 1986).
  • the surfactant contained in the ink composition of the present invention will be described.
  • adjusting the liquid properties of the ink, such as surface tension, by including a surfactant it improves the ejection stability of the ink, and is excellent in improving the water resistance of images and preventing bleeding of printed ink. Has an effect.
  • the surfactant examples include a fatty acid salt, an alkyl sulfate ester salt, an alkylbenzene sulfonate salt, an alkylnaphthylene sulfonate salt, a dialkyl sulfosuccinate salt, an alkyl phosphate ester salt, and a naphthalene sulfonate formalin condensate.
  • anionic surfactants such as polyoxyethylene alkyl sulfates, cationic amines such as fatty amine salts, quaternary ammonium salts, and alkylpyridinium salts, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl ethers Oxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block Polymers, nonionic surface active agents such as acetylene-based polyoxyethylene O sulfoxide, amino acid type amphoteric surfactants Baie evening-in type or the like, fluorine based, and the like silicon compound.
  • anionic surfactants such as polyoxyethylene alkyl sulfates, cationic amines such as fatty amine salts, quaternary ammonium salts, and
  • a nonionic surfactant is preferred from the viewpoint of the above effects, and a nonionic surfactant is more preferred from the viewpoint of ink ejection stability and permeability to paper.
  • a compound represented by the following general formula (I) or ( ⁇ ) or the general formula (III) is more preferable.
  • R 210 -CH 2 CH 20 -h-H In the general formula (I), R 21 represents an alkyl group having 5 to 40 carbon atoms, preferably 8 to 18 carbon atoms, and is a straight chain. Or branched, and may be substituted.
  • Examples of the group that can be substituted for the alkyl group represented by R 21 include an aryl group (for example,
  • alkyl group represented by R 21 examples include n-pentyl, n-hexyl, n-octynole, n-decyl, n-dodecyl, n-pencil dessole, n-octyldecyl, 2 —Ethylhexyl, 1-ethylpentyl, 1-n-butylpentyl, 1-n-pentylhexyl, 1-n-hexylheptyl, 1-n-heptyloctyl, 1-n-octylnonyl, 6-methoxyhexyl, 2 — Phenylethyl and the like.
  • mi represents the average number of moles of ethylene oxide added, and is 2 to 40, preferably 3 to 30 and particularly preferably 3 to 20.
  • R 22 and R ⁇ ⁇ each represent a saturated hydrocarbon having 4 to 10 carbon atoms, and the total number of carbon atoms of R 22 and R 23 is 8 to 18. Represents the average number of moles of ethylene oxide added, and is 3 to 20.
  • Total number of carbon atoms of R 22 and R 23 is 8-1 8, preferably to 8-1 6 Gasara. Is 3 to 20, more preferably 5 to 20 and even more preferably 6 to 18.
  • R 24 represents an alkyl group having 5 to 40 carbon atoms, preferably 5 to 30 carbon atoms, and may be linear or branched, and may be substituted. Is also good.
  • Examples of groups that can be substituted for the alkyl group represented by R M include aryl groups (eg, phenyl, o-tolyl, p-tolyl, p-t-butylphenyl), alkoxy groups (eg,
  • alkyl group represented by R 24 include n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pencil decyl, and n-octyl decyl , 2-ethylhexyl, 1-ethylpentyl, 1-n-butylheptyl, 1-n-hexylnonyl, 1-n-heptyldecyl, 1-n-octyldodecyl, 1-n-decyltetradecyl, 6-methoxy Cyhexyl, 2-phenylethyl and the like can be mentioned.
  • m 2 represents an average addition number of Echirenokishido is 2-4 0, preferably 3-3 0, especially preferably 4 to 2 0.
  • R 25 and R 26 are each a saturated hydrocarbon group having 2 to 20 carbon atoms, and preferably have 4 to 13 carbon atoms.
  • Examples of the saturated hydrocarbon group having 2 to 20 carbon atoms represented by R 25 and R ffi include ethyl, n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. , 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl, n-octyldecyl and the like.
  • m 21 represents an average addition mole number of Echirenokishido is 2-4 0, 3-3 0 are preferred.
  • specific examples of the compound represented by Formula (II) are shown, but the invention is not limited thereto.
  • Examples of the compound represented by the general formula (II-I) include a one-terminal ester of polyethylene oxide of 2-butyloctanoic acid and a polyethylene oxide adduct of decane-16-ol.
  • Table 2 below shows specific examples of the compound represented by the general formula (II-11), but the compound is not limited thereto.
  • the compound represented by the general formula (I) or the general formula (II) can be synthesized using a known method. For example, Takehiko Fujimoto's revised edition, “New 'Surfactant primer'”
  • R 31 and R 32 each independently represent an alkyl group having 1 to 18 carbon atoms.
  • alkyl group having 1 to 8 carbon atoms represent , May be substituted.
  • substituents include an alkyl group (eg, methyl, ethyl, isopropyl, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), a halogen atom (eg, a chlorine atom, a bromine atom) and the like.
  • R 31 and R 32 are preferably an unsubstituted straight-chain alkyl group having 1 to 12 carbon atoms or an unsubstituted branched alkyl group, and particularly preferred examples are methyl, ethyl, and n-butyl. , 2-methylbutyl and 2,4-dimethylpentyl.
  • I ⁇ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and the alkyl group or the phenyl group may be substituted.
  • the substituent of the alkyl group of R 33 an alkyl group (e.g., methyl, Echiru, isoproterenol buildings, etc.), an alkoxy group (e.g., methoxy, ethoxy, etc.), can be exemplified phenyl group.
  • the substituent of the phenyl group of R 33 (For example, methyl, Echiru, isopropyl, etc.) alkyl group, an alkoxy group (e.g., methoxy, ethoxy, etc.), a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom) And the like.
  • R 33 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.
  • X is a hydrogen atom
  • R 34 R 35 each independently represents an alkyl group having 1 to 18 carbon atoms. Preferred substituents and specific examples of R 34 R 35 are substituents and specific examples selected from the same group as R 31 R 32 described above.
  • R 36 represents a hydrogen atom, an alkyl group having 16 carbon atoms, or a phenyl group, and preferred specific examples thereof are substituents and specific examples selected from the same group as R 33 described above.
  • m 3 m 4 represents the average number of moles of ethylene oxide added, and m 3 + m 4 is 0 100, preferably 0 to 50, and particularly preferably 0 to 40.
  • R 33 represents a hydrogen atom
  • R 36 represents a hydrogen atom
  • X represents a hydrogen atom
  • m 3 1100, preferably 150, particularly preferably 1 to 40.
  • R 37 R 38 R 39 and R 40 each independently represent an alkyl group having 16 carbon atoms, preferably 14 carbon atoms.
  • m 31 and m 41 each represent the number of caromoles of ethylene oxide, and their sum is 0 40, preferably 2 20 c or less, and can be represented by the general formula (III) or the general formula (III-1) )), But specific examples of the compound are shown below, but the invention is not limited thereto.
  • the compound represented by the general formula (III) or the general formula (III-1) can be synthesized using a known method.
  • a fully-edited version by Takehiko Fujimoto, “Introduction to New Surfactants” (1992) Can be obtained by the method described on pages 94-107.
  • the compound represented by the general formula (III) or (III-1) can be easily obtained as a commercial product, and its specific trade name is safinol 61, 82, or 104, 420, 440, 465, 485, 504, CT-111, CT-121, CT-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF-37, DF- 58, DF-75, DF-11 0D, DF-210, GA, 0P-340, PSA-204, PSA-216, PSA-336, SE, SE-F, Dynol 604 (Nissin Chemical Co., Ltd.) And Air Products & Chemicals), Orufin A, B,
  • an acetylene-based ethylene oxide adduct (SURFYNOL series (Air Products & Chemi ca 1s)) is preferable, and among them, the molecular weight is particularly preferable. Those having a molecular weight of 200 to 1,000 are preferable, those having a molecular weight of 300 to 900 are more preferable, and those having a molecular weight of 400 to 900 are particularly preferable.
  • the surfactant contained in the ink composition of the present invention it is preferable that precipitation or separation from the ink does not easily occur and the foaming property is low. From this viewpoint, the hydrophobic portion has a double chain or a hydrophobic portion.
  • Branched anionic surfactants anionic or nonionic surfactants having a hydrophilic group near the center of the ⁇ 3 ⁇ 4 ⁇ 3 ⁇ 4 site, and a double-stranded hydrophobic site or a branched hydrophobic site
  • Nonionic surfactants are preferred. Of these, nonionic surfactants are preferred. From this viewpoint, nonionic surfactants having two or more branched 3 ⁇ 4? K moieties or a branched hydrophobic moiety are represented by the general formula (1-1) or the general formula (1-1).
  • the compound represented by the general formula (III-11) is preferably a compound represented by the formula (III-1) or a nonionic surfactant having a hydrophilic group near the center of the hydrophobic site.
  • the content of the surfactant in the ink composition of the present invention is 0.05 to 50 g / L, preferably 0.05 to 30 g / L, and more preferably 0.1 to 20 g / L.
  • the amount of the surfactant in the ink composition is less than 0.05 g / L, the printing quality tends to be remarkably deteriorated, such as a decrease in ejection stability, occurrence of bleeding during color mixing, and occurrence of whiskers.
  • the surfactant in the ink composition is more than 5 Og / L, printing failure may be caused by ink adhesion to the hard surface at the time of ejection.
  • the static surface tension of the ink of the present invention at 25 ° C is preferably 20 mN / m or more, and more preferably 25 mN / m or more. Further, at 25 ° C, it is preferably 60 mN / m or less, more preferably 50 mN / m or less, and particularly preferably 40 mN / m or less.
  • the anti-drying agent and the anti-penetration agent will be described.
  • an anti-drying agent to prevent clogging due to the drying operation at the ink ejection port or a penetration enhancer to allow the ink to penetrate the paper better.
  • a water-soluble organic solvent having a lower vapor pressure than water is preferable.
  • Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene Polyhydric alcohols represented by glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) Lower alkyl ethers of polyhydric alcohols such as ethers, heterocycles such as 2-pyrrolidone, N-methyl-1-pyrrolidone, 1,3-dimethyl-12-imidazolidinone, N-ethylmorpholine, sulfolane, dimethyl sulfo Kiss And polyfunctional
  • penetration enhancers examples include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, etc., sodium lauryl sulfate, and sodium oleate.
  • Alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, etc., sodium lauryl sulfate, and sodium oleate.
  • Nonionic surfactants and the like can be used. These are preferably used within the range of the addition amount that does not cause printing bleeding or paper loss (print-through).
  • a compound represented by the following general formula (VI) as a drying inhibitor or a penetration enhancer.
  • R 41 represents an alkyl group having 1 to 4 carbon atoms
  • R 42 represents an alkyl group having 2 to 3 carbon atoms
  • n represents an integer of 2 to 5.
  • Specific examples of the compound represented by the general formula (VI) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol
  • Examples thereof include rumonobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. Of these, triethylene glycol monobutyl ether and diethylene glycol monobutyl ether are preferred, and triethylene glycol monobutyl ether is particularly preferred.
  • the compound represented by the general formula (VI) is preferably contained in the ink composition in an amount of 5 to 50% by mass, more preferably 10 to 40% by mass.
  • the monohydric or dialkyl ether of the above-mentioned polyhydric alcohol has a surfactant property
  • these are regarded as a drying inhibitor or a penetration enhancer, and are not regarded as the surfactant described above.
  • a dye is dissolved and / or dispersed in an aqueous medium, a specific amount of a surfactant is further added, and additives such as an anti-drying agent and an anti-penetration agent are added as necessary.
  • aqueous medium in the present invention means water or a mixture of water and a small amount of a water-miscible organic solvent to which additives such as a wetting agent, a stabilizer and a preservative are added as necessary.
  • water-miscible organic solvents examples include alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol).
  • alcohols e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol.
  • polyhydric alcohols e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol.
  • glycol derivatives (Eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene
  • glycol monomethyl ether 95 Len glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene Glycol monoethyl ether, ethylene glycol monophenyl ether), amines (for example, ethanolamine, jetanolamine, triethanolamine, N-methylethylamine, N-ethylethylamine, morpholin, N-ethylmorpholine) , Ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethinolepropylenediamine ) And other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone,
  • the dye of the present invention is an oil-soluble dye
  • it can be prepared by dissolving the oil-soluble dye in a high-boiling organic solvent and emulsifying and dispersing it in an aqueous medium.
  • a surfactant may be emulsified and dispersed at the same time as the oil-soluble dye to allow the oil-soluble dye and the surfactant to coexist in the same oil droplets.
  • the surfactant may be dissolved or dispersed in an aqueous medium, but it is preferable that the surfactant coexists with the oil-soluble dye in the same oil droplet.
  • the high-boiling organic solvent refers to a solvent having a boiling point of 150 ° C. or higher, but preferably a solvent having a boiling point of 170 ° C. or higher.
  • fluoric acid esters eg, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethyl hexyl phthalate, decyl phthalate, bis (2,4-di-tert- Amyl phenyl) isophthalate, bis (1,1-ethylpropyl) phthalate), phosphoric acid or phosphonic esters (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl) Phosphate, Jokchi
  • high-boiling organic solvents can be used alone or in mixtures of several types (for example, tricresyl phosphate and dibutyl phosphate, trioctyl phosphate and di (2-ethylhexyl) sebacate, dibutyl phosphate and poly (N —T-butylacrylamide)]].
  • the high-boiling organic solvent can be used in an amount of preferably 0.01 to 3.0 times, more preferably 0.01 to 1.0 times by mass, the oil-soluble dye.
  • the oil-soluble dye and the high-boiling organic solvent are used after being dispersed in an aqueous medium.
  • a low-boiling organic solvent may be used from the viewpoint of emulsifiability.
  • the low-boiling organic solvent include organic solvents having a boiling point of about 30 ° C or higher and 150 ° C or lower at normal pressure.
  • esters eg, ethyl acetate, petiyl acetate, ethyl propionate, ethoxyshethyl acetate, methyl cellosolve acetate
  • alcohols eg, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol
  • ketones For example, methyl isopropyl ketone, methyl ethyl ketone, cyclohexanone
  • amides eg, dimethylformamide, N-methylpyrrolidone
  • ethers eg, tetrahydrid
  • Emulsification dispersion involves dispersing the oil phase, in which the dye is dissolved in a mixed solvent of a high-boiling organic solvent and, in some cases, a low-boiling organic solvent, in an aqueous phase mainly composed of water, to create fine oil droplets of the oil phase. It is done for.
  • an additive such as a surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, a preservative, or a P-type fungicide described below is added to one or both of the aqueous phase and the oil phase as necessary. Can be attached.
  • a method of adding an oil phase to an aqueous phase is generally used.
  • a so-called phase inversion emulsification method in which an aqueous phase is dropped into an oil phase can also be preferably used.
  • the above-mentioned surfactant when emulsifying and dispersing, can be used.
  • Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan
  • Nonionic surfactants such as fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethyleneoxypropylene block copolymers are preferred.
  • SURFYNOLS Air Practs & Chemicons
  • Aminoxide-type amphoteric surfactants such as N, N-dimethyl-N-alkylamineoxide are also preferable.
  • a water-soluble polymer can be added in combination with the above-mentioned surfactant for the purpose of stabilizing immediately after emulsification.
  • the water-soluble polymer polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide, and copolymers thereof are preferably used. It is also preferable to use natural water-soluble polymers such as polysaccharides, casein, and gelatin. Further stability of dye dispersion
  • the polymer preferably contains C 00 —.
  • the polymer is preferably used in an amount of 20% by mass or less, more preferably 10% by mass or less of the high boiling point organic solvent.
  • the volume average particle size is preferably 1 ⁇ m or less, more preferably 5 to: I 0 O nm.
  • the methods of measuring the volume average particle size and the particle size distribution of the dispersed particles include static light scattering, dynamic light scattering, centrifugal sedimentation, and experimental chemistry course, 4th edition, pp. 417-418. It can be easily measured by a known method such as using the described method. For example, dilute the ink with distilled water so that the particle concentration in the ink becomes 0.1 to 1% by mass, and easily use a commercially available volume average particle size analyzer (for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.)). Can be measured. Further, the dynamic light scattering method utilizing the laser Doppler effect is particularly preferable since the particle size can be measured down to a small size.
  • the volume average particle diameter is the average particle diameter weighted by particles # «, and is the sum of the diameters of individual particles multiplied by the volume of the particles in the set of particles divided by the total volume of the particles It is.
  • the average particle size of the Yomizu is described in “Chemistry of Polymer Latex” (Munei Muroi, Polymer Publishing Association).
  • a known centrifugal separation method, a microfiltration method, or the like can be used as a method for removing these coarse particles. These separation means may be performed immediately after emulsification and dispersion, or may be performed immediately after filling various kinds of additives such as a wetting agent and a surfactant into the emulsified dispersion and then filling the ink cartridge.
  • a mechanical emulsifying device As an effective means for reducing the average particle size and eliminating coarse particles, a mechanical emulsifying device can be used.
  • emulsifying device known devices such as a simple stirrer, an impeller single stirring system, an in-line stirring system, a mill system such as a colloid mill, and an ultrasonic system can be used, but the use of a high-pressure homogenizer is particularly preferable. .
  • the high-pressure homogenizer is described in detail in US Pat. No. 4,533,254 and Japanese Patent Application Laid-Open No. 6-47264, but commercially available devices include Gorin Homogenizer— (APV GAUL IN INC.), Microfluidizer. MICRO FLU ID EX INC., ULTIMIZER-1 (Sugino Machine Co., Ltd.), etc.
  • a high-pressure homogenizer having a mechanism for forming fine particles in an ultra-high-pressure jet stream as described in US Pat. No. 5,720,551 is particularly effective for the emulsification dispersion of the present invention.
  • DeBEE 2000 (BEE INTERNATIONAL LTD.) Is an example of an emulsifier using this ultrahigh-pressure jet stream ⁇ ).
  • the pressure at the time of emulsification by the high-pressure emulsifying and dispersing device is 5 OMPa or more, preferably 60 MPa or more, more preferably 18 OMPa or more.
  • a low-boiling organic solvent is contained in addition to the high-boiling organic solvent, it is preferable to remove the low-boiling solvent from the viewpoint of the stability and safety and health of the emulsion.
  • Various known methods can be used to remove the low boiling point solvent depending on the type of the solvent. That is, the evaporation method,
  • This step of removing the low boiling organic solvent is preferably performed as soon as possible immediately after emulsification.
  • the ink composition obtained in the present invention is used for ink jet recording, etc.
  • a UV absorber an antioxidant, a viscosity modifier, a dispersant, a dispersion stabilizer, an antifungal agent, an antibacterial agent, and a pH control.
  • Additives such as an agent, an antifoaming agent and a chelating agent can be appropriately selected and used in an appropriate amount.
  • Examples of the ultraviolet absorber used in the present invention to improve the storability of an image include JP-A-58-185670, JP-A-61-90537, and JP-A-Hei.
  • antifungal agent used in the present invention examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazoline-3-one. And salts thereof. These are preferably used in the ink in an amount of from 0.02 to 5.0% by mass. The details of these are described in "Encyclopedia of Bacterial and Fungicides" (edited by the Japanese Society of Bacteria and Fungi).
  • antibacterial agent examples include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, benzotriazol and the like. These are preferably used in the ink in an amount of from 0.02 to 5.0% by mass.
  • the pH adjusting agent used in the present invention can be suitably used in terms of pH adjustment, dispersion stability imparting, etc., and is preferably added so as to have a pH of 4.5 to 10.0. More preferably, it is added so as to be ⁇ 10.0.
  • Examples of the pH adjuster include basic ones such as organic bases and inorganic alkalis, and acidic ones such as organic acids and inorganic acids.
  • the above three organic bases include triethanolamine, diethanolamine, N-methyljetanolamine, dimethylethanolamine and the like.
  • Examples of the above-mentioned inorganic alkali include hydroxides of alkali metals (eg, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (eg, sodium carbonate, sodium hydrogencarbonate, etc.), and ammonia.
  • Examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid.
  • Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid.
  • the viscosity of the ink of the present invention is preferably 3 OmPa-s or less. Further, since it is more preferable to adjust the viscosity to 2 OmPas or less, a viscosity modifier may be used for the purpose of adjusting the viscosity.
  • a viscosity adjuster include water-soluble polymer nonionic surfactants such as celluloses and polyvinyl alcohol. For more details, see Chapter 9 of “Viscosity Adjusting Technology” (Technical Information Association, 1999), and “Chemicals for Inkjet Pudding Yuichi (98 Supplement) —Material Development Trends / Prospect Survey I” (CMC, 1997) Year) pages 162 to 174.
  • the above-mentioned various cationic, anionic and nonionic surfactants are used as dispersants and dispersion stabilizers, and chelating agents such as fluorinated and silicone compounds and EDTA are also used as defoaming agents, if necessary. Can be used.
  • chelating agents such as fluorinated and silicone compounds and EDTA are also used as defoaming agents, if necessary. Can be used.
  • the support for recording paper and film consists of chemical pulp such as LBKP, NB KP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, CGP, waste paper pulp such as DIP, etc.
  • chemical pulp such as LBKP, NB KP
  • mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, CGP
  • waste paper pulp such as DIP, etc.
  • Additives such as a sizing agent, a fixing agent, a cationic agent, and a paper strength agent are mixed, and those manufactured by various apparatuses such as a fourdrinier paper machine and a circular net paper machine can be used.
  • Other synthetic paper these supports may be any of a plastic film sheet, thickness 1 0-2 5 0 ⁇ M the support, the basis weight 1 0 ⁇ 2 5 0 gZm 2 is desirable.
  • An image receiving material may be provided by directly providing an image receiving layer and a nome coat layer on a support, or a size press or an anchor coat layer may be provided with starch or polyvinyl alcohol, and then an image receiving layer and a back coat layer may be provided to provide an image receiving material. Is also good. Further, the support may be subjected to a flattening process using a calendar device such as a machine calendar, a TG calendar, and a soft calendar.
  • a calendar device such as a machine calendar, a TG calendar, and a soft calendar.
  • polyolefin eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof
  • polyolefin eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof
  • a white pigment eg, titanium oxide, dumbbell oxide
  • a coloring dye eg, cobalt blue, ultramarine, neodymium oxide
  • white pigments include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithobone, zeolite, barium sulfate, calcium sulfate, and titanium dioxide.
  • inorganic pigments such as zinc sulfide and zinc carbonate, and organic pigments such as styrene-based pigments, acrylic pigments, urea resins, and melamine resins.
  • organic pigments such as styrene-based pigments, acrylic pigments, urea resins, and melamine resins.
  • a porous white inorganic pigment particularly preferred is synthetic amorphous silica having a large pore area.
  • synthetic amorphous silica both silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid. Two or more of these pigments may be used in combination.
  • aqueous binder contained in the image receiving layer examples include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, and zeolite.
  • Water-soluble polymers such as latin, carboxymethylcellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives, and water-dispersible polymers such as styrene butadiene latex and acryl emulsion No.
  • aqueous binders can be used alone or in combination of two or more.
  • polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer.
  • the image-receiving layer may contain a mordant, a water-proofing agent, a light-fastness improver, a surfactant, a hardener and other additives in addition to the pigment and the aqueous binder.
  • the mordant added to the image receiving layer is preferably immobilized.
  • a polymer mordant is preferably used.
  • An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-1-161236 is particularly preferred.
  • the use of the polymer mordant described in the publication makes it possible to obtain an image with excellent image quality and to improve the light fastness of the image.
  • the water-proofing agent is effective for making the image water-resistant, and as such a water-proofing agent, a thiothion resin is particularly desirable.
  • a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiarylammonium chloride polymer, cationic polyacrylamide, and colloidal silica.
  • polyamide polyamine epichlorohydrin is preferred. The content of these cationic resins depends on the ink receiver.
  • It is preferably from 1 to 15% by mass, more preferably from 3 to 10% by mass, based on the total solid content of the vessel.
  • the light resistance improver examples include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzophenone and benzotriazole ultraviolet absorbers. Of these, zinc sulfate is particularly preferred.
  • Surfactants function as coating aids, release improvers, slipperiness improvers, or antistatic agents.
  • the surfactants are described in JP-A Nos. 62-173,463 and 62-183,457.
  • organic fluoro compound may be used in place of the surfactant.
  • the organic fluoro compound is preferably hydrophobic.
  • organic fluoro compounds include fluorinated surfactants, oily fluorinated compounds (eg, fluorinated oils), and solid fluorinated compound resins (eg, tetrafluoroethylene resin).
  • fluorinated surfactants e.g., oily fluorinated compounds
  • solid fluorinated compound resins eg, tetrafluoroethylene resin.
  • the materials described on page 222 of JP-A No. 11-31632 can be used.
  • the image receiving layer may be a single layer or two layers.
  • the recording paper and the recording film may be provided with a back coat layer.
  • examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components.
  • Examples of the white pigment contained in the pack coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, sachin white, and silicic acid.
  • Pigment polyethylene, microcapsules, organic pigments such as urea resin and melamine resin.
  • the aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, Examples include water-soluble polymers such as latin, carboxymethylcellulose, hydroxyethylcellulose, and polyvinylpyridone, and water-dispersible polymers such as styrene-butadiene latex and acrylacryl emulsion.
  • Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.
  • a polymer-fine particle dispersion may be added to the constituent layers (including the back layer) of the ink jet recording paper and the recording film.
  • the polymer fine particle dispersion is used for the purpose of improving film properties such as dimensional stability, curling prevention, adhesion prevention, and film crack prevention.
  • the polymer fine particle dispersion is described in Japanese Patent Publications Nos. 624-245258, 623-136664, and 621-110666. is there. When a polymer fine particle dispersion having a low glass transition temperature (40 ° C or less) is added to a layer containing a mordant, cracking and curling of the layer can be prevented.
  • the ink composition of the present invention can be used as, for example, a display image material other than ink jet recording, an image forming material of an interior decoration material, and an image forming material of an outdoor decoration material.
  • Display image materials include posters, wallpapers, decorative accessories (such as figurines and dolls), commercial flyers, wrapping paper, wrapping materials, paper bags, vinyl bags, package materials, signboards, and transportation ( (Cars, buses, trains, etc.) refers to various things such as images drawn or attached to the side of the car, clothes with logos, etc.
  • the dye of the present invention is used as a material for forming a display image, the image is not limited to an image in a narrow sense, and includes all patterns of a human-recognizable dye, such as abstract designs, characters, and geometric patterns.
  • upholstery materials include wallpaper, decorative accessories (such as figurines and dolls), lighting fixtures,
  • the image is not limited to an image in a narrow sense, and includes all patterns of a human-recognizable dye, such as abstract designs, characters, and geometric patterns.
  • Outdoor decoration materials refer to various materials such as wall materials, roofing materials, signboards, gardening materials, outdoor decoration accessories (such as figurines and dolls), and members of outdoor lighting equipment.
  • the dye of the present invention is used as an image forming material, not only the image in the narrow sense but also the pattern of the dye which can be perceived by humans, such as abstract designs, characters, and geometric patterns. All included.
  • examples of the medium on which the pattern is formed include paper, fiber, cloth (including nonwoven fabric), plastic, metal, and ceramics.
  • the dyeing form the dye can be immobilized in the form of mordanting, printing, or a reactive dye having a reactive group introduced therein. Among these, dyeing is preferably performed in a mordant form.
  • Deionized water was added to the following components to make it 1 hour, and then stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 1 Omo 1/1, and the mixture was filtered under reduced pressure through a microfil having an average pore diameter of 0.25 ⁇ m to prepare a light cyan ink liquid.
  • Phthalocyanine cyan dye (Exemplified compound 154) 8.75 g / 1 Gethylene glycol 130 71 Glycerin 150 g / l Triethylene glycol monobutyl ether 130 g / 1 Triethanolamine 6.0 g / 1 Penzotriazole 0. 08 g / 1
  • Ink sets 102 to 108 were prepared in the same manner as the ink set 101 except that the dye type and the surfactant were changed according to Table 4 below. The amount of the surfactant added was 1.0 mass% in all cases. Also, an ink set 109 of a comparative example was prepared with the same formulation as the ink set 101 except that the dye type was changed to A-2 described above. Further, an ink set 110 of a comparative example was prepared using the same formulation as the ink set 101 except that the surfactant was not used.
  • the oxidation potential of the dye represented by the general formula (C-I) was higher than 1.0 V, and the oxidation potential of Dye A-2 was about 0.76 V.
  • these ink sets 101 to 110 are packed in ink jet pudding PM670C (EPSON) cartridges, and the same machine is used to print images on Fuji Photo Film Co., Ltd. ink jet paper per photo glossy paper EX. Printed and rated below o
  • the force cartridge was set at the time of printing and the ejection of ink from all the nozzles was confirmed. After that, 20 sheets of A4 paper were output and evaluated according to the following criteria.
  • the obtained image was immersed in deionized water for 10 seconds, and then the image size was evaluated.
  • the light fastness was determined by measuring the image density (initial reflection density) Ci immediately after printing using an X-rite 310, and then applying xenon light (85,000 lux) to the image using an Atlas Weather Meter. After irradiation on the day, the image density Cf was measured again, and the residual dye ratio Cf / Ci * 100 was determined and evaluated. The initial reflection density was evaluated at three points of 1, 1.5, and 2 with respect to the dye persistence. A: When the dye residual rate was 70% or more at any density, A: When the two points were less than 70% Is B, and C is less than 0% at all concentrations.
  • MI CROFLUIDEX MI CROFLUIDEX
  • the dye type and high boiling point organic solvent used were changed, and the ink set 201 shown in Table 5 below was used for mazen evening ink, light mazen evening ink, cyan ink, and yellow ink.
  • the ink sets 202 to 208 were prepared in the same manner as the ink set 201 except that the dye type and the surfactant were changed according to Table 6 below.
  • the amount of the surfactant added was 1.0 mass% in all cases.
  • an ink set 209 of a comparative example was prepared with the same formulation as the ink set 201 except that the dye type was changed to C-1 described above.
  • an ink set 210 of a comparative example was prepared with the same formulation as the ink set 201 except that the surfactant was removed.
  • the oxidation potential of the dye represented by the general formula (C-I) was higher than 1.0 V, and the oxidation potential of Dye C-1 was about 0.99 V.
  • these ink sets 101 to 110 were packed in cartridges of an ink jet printer PM670C (manufactured by EPSON), and the same machine was used to print images on inkjet photo paper glossy paper EX manufactured by Fuji Photo Film Co., Ltd. The same evaluation as in Example 1 was performed. The results obtained are shown in Table 6 below.
  • Deionized water was added to the following components, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with K0H1 Omo 1/1, and the mixture was filtered under reduced pressure through a microfil having an average pore diameter of 0.25 ⁇ m to prepare an ink solution for light cyan.
  • Phthalocyanine cyan dye (Exemplified compound 154) 8.75 g / l Diethylene glycol 130 g / l Glycerin 150 g / l Triethylene glycol monobutyl ether 130 g / l Trienol noramine 6. Og / 1 Benzotriazole 0.08 g / 1
  • the ink sets 302 to 208 were prepared in the same manner as the ink set 301 except that the dye type and the surfactant were changed according to Table 8 below.
  • the amount of added calories of the surfactants was all adjusted to 1.0% by mass.
  • An ink set 309 was prepared in the same manner as the ink set 301 except that triethylene glycol monobutyl ether was not used.
  • the ink composition of Comparative Example was the same formulation as the ink set 301.
  • An ink set 311 of a comparative example was prepared using the same formulation as the ink set 301 except that the dye type was changed to A-2.
  • An ink set 312 of Comparative Example was prepared using the same formulation as the ink set 301 except that the surfactant and triethylene glycol monobutyl ether were omitted.
  • Fine line bleeding 1 was printed by printing yellow, magenta, cyan and black fine line patterns and evaluated visually.
  • bleeding 2 of fine lines black was printed with cyan ink in the evening, black fine lines were printed, and bleeding due to contact between the two colors was also evaluated.
  • the obtained image was immersed in deionized water for 10 seconds, and then the bleeding of the image was evaluated.
  • the light fastness was determined by measuring the image density (initial reflection density) Ci immediately after printing using an X-rite 310, and then using an Atlas Weather Meter to apply xenon light (85,000 l) to the image.
  • the dye reflection ratio was evaluated at three points where the initial reflection density was 1, 1.5, and 2.A dot was obtained when the dye remaining ratio was 90% or more at any density.
  • the case was B and the case where the concentration was less than 90% at all concentrations was C.
  • MI CROFLUIDEX MI CROFLUIDEX
  • Additives such as 140 g of dimethylene glycol, 64 g of glycerin, 16 g of a surfactant (W5-4), and urea are added to the thus obtained oil-soluble dye fine milky sardine.
  • Light cyan ink according to Table 9 below was prepared by adjusting the pH to 9 with 90 Oml of water and KOH 1 Omo 1/1. The volume-average particle size of the resulting dairyo-dispersed ink was measured using a Microtrac UPA (Kikki Co., Ltd.) and found to be 62 nm.
  • Example 9 a magenta ink, a light magenta ink, a cyan ink, a yellow ink, and a black ink of ink set 401 shown in Table 9 below were produced.
  • the structures of the high-boiling organic solvent and the dye represented by the same symbols as in Example 2 are the same as those shown in Example 2.
  • ink sets 402 to 408 were prepared in the same manner as ink set 401 except that the dye type and the surfactant were changed according to Table 10 below.
  • the amount of the surfactant added was all 1.0 mass%.
  • An ink set 409 was prepared in the same manner as the ink set 401 except that triethylene glycol monobutyl ether was not used.
  • the ink of Comparative Example was prepared in the same formulation as Ink Set 401.
  • An ink set 410 was produced.
  • An ink set 411 of a comparative example was prepared in the same manner as the ink set 401 except that the dye type was changed to C-1. In addition, except that the surfactant and triethylene glycol monobutyl ether were excluded, the ink set 40 was used.
  • Ink Set 412 of Comparative Example was prepared using the same formulation as 1.
  • the oxidation potential of the dye represented by the general formula (C-I) was higher than 1.0 V, and the oxidation potential of Dye C-1 was about 0.99 V.
  • these ink sets 401 to 412 are packed in a cartridge of Inkjet Pudding Yuichi PM 670C (manufactured by EPSON), and the image is printed on inkjet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd. Then, the same evaluation as in Example 3 was performed.
  • Examples 1 to 4 show that the ink composition of the present invention is excellent in all of ejection stability, weather resistance (fastness to light and heat) and water resistance, and can provide an image without blurring of fine lines. Further, the ink composition (ink set 109, 209, 311, 411) using a dye other than the dye of the present invention (oxidation potential is nobler than 1.0 V) and containing a surfactant has good ejection stability. And an ink composition containing only the dye of the present invention (ink set 110, 210, 310, 312, 410, 412).
  • one two Three can be said to be excellent in light resistance, but in water resistance and bleeding, good results are obtained for the first time by the ink composition of the present invention containing both the dye of the present invention and a surfactant. You can see that. Further, it can be seen that the use of triethylene glycol monobutyl ether (the compound represented by the general formula (IV)) improves the ejection stability, bleeding of fine lines, and particularly the performance of intermittent ejection.
  • Deionized water was added to the following components to make the mixture one night and one hour, followed by stirring at 30-40 ° C for 1 hour while heating.
  • the mixture was filtered under reduced pressure through a microfill having an average pore diameter of 0.25 / m to prepare an ink solution for lithocyan.
  • Phthalocyanine cyan dye (Exemplified Compound 154) 17.5 g / L diethylene glycol 164 g / L glycerin 123 g / L triethylene glycol monobutyl ether 119 g / L triethanolamine 6.5 g / L benzotriazole 0.07 g / L
  • PROXEL XL 2 3.5 g / L surfactant (1) 10 g / L surfactant (1): One-terminal 2-butyloctanoate of polyethylene glycol (average number of repeating ethylene oxide 10)
  • magenta dye azo dye, Exemplified Compound a-36
  • yellow dye black dye instead of cyan dye as the dye type
  • changing the additives mazen evening ink, light mazen evening ink
  • the ink set 501 shown in Table 11 was prepared by adjusting the cyan ink, yellow ink, dark yellow ink, and black ink.
  • the structure of the dye represented by the same symbol as in Example 1 is the same as that shown in Example 1.
  • ink sets 502 to 507 were prepared in the same manner as in 501 except that the dye type, surfactant type, and additive amount of light cyan and cyan ink of ink set 501 were changed according to Table 12 below. .
  • the oxidation potential of the dye (154) represented by the general formula (C-I) is higher than 1.0 V, and the oxidation position of the dye A-2 is about 0.1.
  • the a was a 76V, in Table 12, the surfactant (2): SURFYN0L465 (Air Product s & Chemicals ne ten.).
  • the ink set 50 :! to 507 manufactured as described above is packed into the ink jet pudding-PM920C (Seiko Epson Corporation) cartridge and
  • the print cartridge was set in the printer every night, and ink ejection from all nozzles was confirmed. After that, 20 sheets of A4 paper were output, and the printing disorder was evaluated.
  • the obtained image was immersed in deionized water for 10 seconds, and then the bleeding of the image was evaluated.
  • the concentration before and after storing the sample for 5 days under the condition of 80 to 70% RH was measured with -rit 6310 to determine the residual dye ratio, and the evaluation was performed.
  • Table 13 shows that when the ink composition of the present invention is used, excellent ejection stability can be obtained, and that the ink composition exhibits excellent performance in terms of water resistance and fastness.
  • the ink of the present invention is excellent in the performance of outputting fine lines without blurring.
  • the inks (501 to 504) of the present invention obtained the same hue as the ink (107).
  • An ink prepared by using another dye represented by the general formula (C-I) in place of the cyan dye (154) in the ink set 501 also has the same effects of fastness, ejection stability and hue as the 501. Obtained.
  • Deionized water was added to the following components, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the solution was filtered under reduced pressure through a microfil filter having an average pore diameter of 0.25 / m to prepare a light magentic ink for evening light.
  • Magenta dye (Exemplified compound a-36) 10.2 g / L Triethylene glycol monobutyl ether 130.0 g / L Glycerin 130.0 g / L Diethylene glycol 150.0 g / L Trienol noramine 7.0 g / L Penzotriazole 0.07 g / L PROXEL XL 2 [Zenekisha] 5.0 g / L surfactant (1) 6.0 g / L surfactant (1): polyethylene glycol (average ethylene glycol) 2-terminal butyl octanoate with a repetition of oxide of 10)
  • Example 1 The structure of the dye represented by the same symbol as in Example 1 is the same as that shown in Example 1.
  • the ink was prepared in the same manner as the ink 601 except that the dye type, the surfactant type, and the additive amount of the additives were changed according to Table 14 below. Sets 602-607 were made.
  • the oxidation potential of the azo dye (a-36) represented by the general formula (M-I) is higher than 1.0 V, and the oxidation potential of the dyes B-1 and B-2 The potential was less than 1.0 V.
  • surfactant (2) SU FYNOL465 (Air Products & Chemicals).
  • Table 16 shows that when the ink composition of the present invention was used, excellent ejection stability was obtained, and that the ink composition also exhibited excellent performance in terms of water resistance and fastness.
  • the ink of the present invention is excellent in the performance of outputting fine lines without blurring.
  • the inks (601 to 504) of the present invention had the same hue as the ink (607).
  • the ink prepared by using another water-soluble dye represented by the general formula (M-I) in place of the magenta dye (a-36) in the ink set 600 has the same robustness as that of the ink. The effects of the properties, ejection stability and hue were obtained.
  • ADVANTAGE OF THE INVENTION in a water-based ink which is advantageous in terms of handleability, odor, safety, etc., it has high ejection stability, good hue, excellent weather resistance and water resistance, and has no bleeding of fine lines.
  • An ink composition from which a recorded image can be obtained and an ink jet recording method using the ink composition can be provided.
  • the ink composition of the present invention can be used in a known ink jet recording system, for example, a charge control system for discharging ink using electrostatic attraction, a drop-on-demand system using the oscillating pressure of a piezo element ( Pressure pulse method), an acoustic ink jet method in which an electric signal is converted to an acoustic beam, and the ink is irradiated to the ink and the ink is ejected using radiation pressure; and the pressure generated by heating the ink to form bubbles is used. It is used in a mar-jet (bubble jet) system.
  • the ink jet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of colorless and transparent ink.
  • the method of use is included, and the ink composition of the present invention is used for any of these.

Abstract

L'invention concerne une composition d'encre caractérisée en ce qu'elle comprend un support aqueux et, dissous ou dispersé dans ce support, au moins un colorant possédant un potentiel d'oxydation plus noble que 1,0 V, et en ce qu'elle contient un tensioactif en une quantité comprise entre 0,05 et 50 g/l. En raison de sa constitution, la composition d'encre possède une stabilité élevée d'arrivée, retient une teinte intacte, et peut donner une image de grande qualité dont la tenue aux intempéries est excellente et dont la résistance à l'eau perdure.
PCT/JP2003/001070 2002-02-04 2003-02-03 Composition d'encre et procede d'impression par jet d'encre WO2003066751A1 (fr)

Priority Applications (3)

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JP2003566110A JP4538228B2 (ja) 2002-02-04 2003-02-03 インク組成物、インクジェット記録方法
EP20030703149 EP1473332B1 (fr) 2002-02-04 2003-02-03 Composition d'encre et procede d'impression par jet d'encre
US10/503,444 US7311391B2 (en) 2002-02-04 2003-02-03 Ink composition and ink jet recording method

Applications Claiming Priority (8)

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JP2002-26838 2002-02-04
JP2002026839 2002-02-04
JP2002-26839 2002-02-04
JP2002026838 2002-02-04
JP2002-34325 2002-02-12
JP2002033984 2002-02-12
JP2002-33984 2002-02-12
JP2002034325 2002-02-12

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WO2003066751A1 true WO2003066751A1 (fr) 2003-08-14

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JP (1) JP4538228B2 (fr)
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WO (1) WO2003066751A1 (fr)

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DE10341647A1 (de) * 2003-09-10 2005-04-21 Klaus Wabbels Flachgründung für ein Gebäude aus einem Leichtbaumaterial und Verfahren zur Herstellung und zum Rückbau der Flachgründung
JP2006089730A (ja) * 2004-08-24 2006-04-06 Fuji Photo Film Co Ltd インク組成物及びインクジェット記録方法
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JP2007217531A (ja) * 2006-02-16 2007-08-30 Brother Ind Ltd インクジェット記録用インクセット
JP2007217528A (ja) * 2006-02-16 2007-08-30 Brother Ind Ltd インクジェット記録用シアンインク
JP2007217525A (ja) * 2006-02-16 2007-08-30 Brother Ind Ltd インクジェット記録用マゼンタインク
JP2007217526A (ja) * 2006-02-16 2007-08-30 Brother Ind Ltd インクジェット記録用シアンインク
JP2007217533A (ja) * 2006-02-16 2007-08-30 Brother Ind Ltd インクジェット記録用インク
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CN100371401C (zh) 2008-02-27
JPWO2003066751A1 (ja) 2005-06-02
US20050081745A1 (en) 2005-04-21
EP1473332A4 (fr) 2005-03-16
EP1473332A1 (fr) 2004-11-03
CN1628156A (zh) 2005-06-15
EP1473332B1 (fr) 2011-05-25
US7311391B2 (en) 2007-12-25
JP4538228B2 (ja) 2010-09-08

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